JPH02166270A - Surface treatment for blade - Google Patents
Surface treatment for bladeInfo
- Publication number
- JPH02166270A JPH02166270A JP32084088A JP32084088A JPH02166270A JP H02166270 A JPH02166270 A JP H02166270A JP 32084088 A JP32084088 A JP 32084088A JP 32084088 A JP32084088 A JP 32084088A JP H02166270 A JPH02166270 A JP H02166270A
- Authority
- JP
- Japan
- Prior art keywords
- blade
- film
- ion
- ion beam
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004381 surface treatment Methods 0.000 title claims description 6
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000005566 electron beam evaporation Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- -1 hydrocarbon ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 235000006693 Cassia laevigata Nutrition 0.000 description 1
- 241000735631 Senna pendula Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229940124513 senna glycoside Drugs 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は刃の表面処理方法、特に電気カミソリ等の刃の
表面に硬質被膜を形成する場合の表面処理方法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for surface treatment of a blade, and particularly to a surface treatment method for forming a hard coating on the surface of a blade of an electric razor or the like.
（従来の技術）
真空中において母材の表面に金属あるいはセラミックス
等の被膜を形成する手段として、例えば物理蒸着法（以
下ｒＰＶＤ法Ｊという）が知られている。とりわけ、母
材の表面に金属の炭化物や窒化物の膜を形成するＰＶＤ
法として、イオンブレーティング・スパッタリングが一
般的である。(Prior Art) For example, a physical vapor deposition method (hereinafter referred to as rPVD method J) is known as a means for forming a film of metal, ceramic, or the like on the surface of a base material in a vacuum. In particular, PVD forms a film of metal carbide or nitride on the surface of the base material.
Ion blasting and sputtering are common methods.
従来、このようなＰＶ、Ｄ法により母材の表面にＴｉＣ
Ｎ膜を形成する場合、例えば特開昭６０−９２４６５号
公報に記載されているように、メタン等の炭化水素ガス
及び窒素ガスを槽内に導入させたプラズマ雰囲気中にて
チタンを蒸着あるいはスパッタリングを行うことにより
被膜が形成されていた。Conventionally, TiC was deposited on the surface of the base material using such PV and D methods.
When forming the N film, titanium is deposited or sputtered in a plasma atmosphere in which a hydrocarbon gas such as methane and nitrogen gas are introduced into a tank, for example, as described in JP-A No. 60-92465. A film was formed by doing this.
（発明が解決しようとする課題）
しかしながら、前述した従来の方法によって母材の表面
にＴｊＣＮ膜を形成する場合、工業レベルにて膜組成や
膜構造を制御するのは必ずしも容易なことではなく、こ
のため品質にバラツキが生しるという問題があった。(Problems to be Solved by the Invention) However, when forming a TjCN film on the surface of a base material using the conventional method described above, it is not necessarily easy to control the film composition and film structure at an industrial level. For this reason, there was a problem of variations in quality.
また、従来の方法をカミソリ刃等に応用した場合、その
耐食性が問題となる場合があり、水分や塩分等の存在す
る腐食雰囲気下にて長時間使用するとサビが発生し易い
という問題があった。In addition, when conventional methods are applied to razor blades, etc., their corrosion resistance may become a problem, and rust is likely to occur if used for a long time in a corrosive atmosphere containing moisture, salt, etc. .
これは、通常のＰＶＤ法により被膜を形成した場合、第
２図に示されるように、刃ｌの表面に形成されたＴｉＣ
Ｎ膜２の内部にはボイドやピンホール等が多数発生し、
これらの欠陥が核となって腐食反応が促進されサビ３が
発生するためと考えられている。When a film is formed by the normal PVD method, the TiC formed on the surface of the blade l is as shown in Fig. 2.
Many voids, pinholes, etc. occur inside the N film 2,
It is thought that these defects act as cores that accelerate corrosion reactions and generate rust 3.
従って、従来の手段によりＴｉＣＮ膜処理を行ったカミ
ソリ刃等が使用されるときは、人間の体質や雰囲気によ
って問題が発生する場合もあり、これを解決する必要が
あった。Therefore, when a razor blade or the like treated with a TiCN film by conventional means is used, problems may occur depending on the human constitution and atmosphere, and it is necessary to solve these problems.
この発明は斯る課題を解決するためになされたもので、
その目的とするところは、母材となる刃の表面に耐食性
に優れたＴｉＣＮ膜を形成することのできる刃の表面処
理方法を提供することにある。This invention was made to solve this problem.
The purpose is to provide a method for surface treatment of a blade that can form a TiCN film with excellent corrosion resistance on the surface of the blade, which is a base material.
（課題を解決するための手段）
前記目的を達成するために、本発明方法においては、表
面に被膜を形成すべき刃を真空槽内に配置し、この刃に
対し炭化水素ガスおよび窒素ガスのイオンビームをそれ
ぞれ照射すると共に、このイオンビーム照射と同時に蒸
発源からチタンを電子ビーム蒸発させ、チタンの形成速
度に対する各イオンビーム密度を制御しながら刃の表面
ＱこＴｉＣＮ膜を形成するようにしたことを特徴とする
。(Means for Solving the Problems) In order to achieve the above object, in the method of the present invention, a blade on which a film is to be formed is placed in a vacuum chamber, and a hydrocarbon gas and nitrogen gas are supplied to the blade. At the same time as each ion beam was irradiated, titanium was evaporated from an evaporation source with an electron beam at the same time as the ion beam irradiation, and a TiCN film was formed on the surface of the blade while controlling the ion beam density with respect to the titanium formation rate. It is characterized by
（作用）
前記構成により、本発明方法は、いわゆるイオンビーム
アシスト蒸着手段により刃の表面にＴｉＣＮ膜を形成す
るものであるが、チタンの形成速度に対して炭化水素ガ
スと窒素ガスのイオンビーム密度とを制御することによ
り、所定の膜組成構造を備えた被膜を得ることができる
。(Function) With the above configuration, the method of the present invention forms a TiCN film on the surface of the blade by so-called ion beam assisted vapor deposition, but the ion beam density of hydrocarbon gas and nitrogen gas is lower than the formation rate of titanium. By controlling this, a film having a predetermined film composition structure can be obtained.
このとき、前記炭化水素ガスと窒素ガスとのイオンビー
ム比を制御することで、工業レベルにて膜組成や膜構造
を容易に制御することができ、このため、耐食性に優れ
、かつバラツキの少ない均質なＴｉＣＮ膜を形成するこ
とが可能となる。At this time, by controlling the ion beam ratio of the hydrocarbon gas and nitrogen gas, the film composition and film structure can be easily controlled at an industrial level, resulting in excellent corrosion resistance and less variation. It becomes possible to form a homogeneous TiCN film.
（実施例） 以下、図面に基づき本発明の詳細な説明する。(Example) Hereinafter, the present invention will be described in detail based on the drawings.
第１図は本発明方法を使用するための装置の概略構成が
示されている。FIG. 1 shows a schematic configuration of an apparatus for using the method of the present invention.
ここで本発明の特徴的なことは、表面に被膜を形成すべ
き刃を真空槽内に配置し、この刃に対し炭化水素ガスお
よび窒素ガスのイオンビームをそれぞれ照射すると共に
、このイオンビーム照射と同時に蒸発源からチタンを電
子ビーム蒸発させ、チタンの形成速度に対する各イオン
ビーム密度を制御しながら刃の表面にＴｉＣＮ膜を形成
するようにしたことである。Here, the characteristic feature of the present invention is that the blade on which a film is to be formed is placed in a vacuum chamber, and the blade is irradiated with ion beams of hydrocarbon gas and nitrogen gas, respectively, and the ion beam irradiation is performed on the blade. At the same time, titanium was evaporated with an electron beam from an evaporation source, and a TiCN film was formed on the surface of the blade while controlling the density of each ion beam with respect to the rate of formation of titanium.
すなわち、本発明はイオンビームアシスト蒸着手段によ
り刃の表面処理を行うものであり、本実施例において、
表面に被膜を形成すべき刃９が真空チャンバ１０内の上
方に配置されている。また、この真空チャンバ１０内の
下方には、電子ビーム等の蒸発源４およびその周囲に２
台のイオン銃５６が設けられている。That is, the present invention performs the surface treatment of the blade by ion beam assisted vapor deposition means, and in this example,
A blade 9 whose surface is to be coated is placed above the vacuum chamber 10 . Further, in the lower part of the vacuum chamber 10, there is an evaporation source 4 such as an electron beam, and two evaporation sources around it.
A base ion gun 56 is provided.
これらのイオン銃５，６のうち、一方のイオン銃５は窒
素ガスボンへ７に接続され、他方のイオン銃６はメタン
やアセチレン等の炭化水素ガスポンへ８に接続されてい
る。Of these ion guns 5 and 6, one ion gun 5 is connected to a nitrogen gas bomb 7, and the other ion gun 6 is connected to a hydrocarbon gas pump 8 such as methane or acetylene.
更に、前記刃９の近傍かつ側方でイオンビームの照射さ
れない領域には、チタン（Ｔｉ）の形成速度を検出する
ための水晶センサＩｆが設けられており、この水晶セン
サ１１の前面には、検出精度を向上させるための中空円
筒状のカバー１２が設けられている。Furthermore, a crystal sensor If for detecting the formation rate of titanium (Ti) is provided in a region near and to the side of the blade 9 that is not irradiated with the ion beam. A hollow cylindrical cover 12 is provided to improve detection accuracy.
前記電子ビーム蒸発源４および膜の形成速度を検出する
ための水晶センサ１１は、膜形成速度制御部１３に接続
されている。The electron beam evaporation source 4 and a crystal sensor 11 for detecting the film formation speed are connected to a film formation speed control section 13.
次に本実施例の作用を説明する。まず、真空チャンバＩ
Ｏ内の上方の所定位置に刃９が設定された後、チャンバ
１０内が２ Ｘｌ０−’Ｐａ以下に真空排気され、続い
て１台又は２台のイオン銃５．６が動作されてクリーニ
ングが行われる。このとき、アルゴン又は窒素等のイオ
ンビームが刃９の表面に照射され、加速電圧として５０
０〜２０００ Ｖ、かつ２〜数１０ ｌＩＡ／ｃｍ”程
度のイオンビームが数分間照射される。Next, the operation of this embodiment will be explained. First, vacuum chamber I
After the blade 9 is set at a predetermined position above the chamber 10, the inside of the chamber 10 is evacuated to 2 Xl0-'Pa or less, and then one or two ion guns 5.6 are operated to perform cleaning. It will be done. At this time, an ion beam of argon or nitrogen or the like is irradiated onto the surface of the blade 9, and the acceleration voltage is 50
An ion beam of 0 to 2000 V and about 2 to several tens of lIA/cm" is irradiated for several minutes.
このようにしてクリーニング作業が行われた後、２台の
イオン銃５．６が動作され、炭化水素ガス及び窒素ガス
のイオンビームがそれぞれ刃９の表面に向は照射される
。また、これらのイオンビーム照射と同時に、蒸発源４
からチタン（Ｔｉ）が刃９の表面に向は電子ビーム蒸発
される。この結果、炭化水素イオン、窒素イオン、チタ
ンが刃９の表面にて反応しＴｉＣＮ膜が形成される。After the cleaning work is performed in this manner, the two ion guns 5.6 are operated, and the surface of the blade 9 is irradiated with ion beams of hydrocarbon gas and nitrogen gas, respectively. Also, at the same time as these ion beam irradiations, the evaporation source 4
Then, titanium (Ti) is evaporated onto the surface of the blade 9 using an electron beam. As a result, hydrocarbon ions, nitrogen ions, and titanium react on the surface of the blade 9 to form a TiCN film.
本実施例において、刃９の表面位置における炭化水素及
び窒素イオンビーム密度は１０〜５００μＡ／ｃｍ２の
範囲で行われ、又チタン（Ｔｉ）の形成速度は、水晶セ
ンサ１１を介して膜形成速度制御部１３により１〜２０
人／Ｓの範囲で制御される。この場合、所定のチタン形
成速度に対して、窒素イオンビーム密度が増加すると赤
味がかった膜が形成され、反対に、炭化水素ガスイオン
ビーム密度が増加すると黒味がかった膜が形成されるこ
とが判明した。In this example, the hydrocarbon and nitrogen ion beam density at the surface position of the blade 9 is carried out in the range of 10 to 500 μA/cm2, and the film formation rate is controlled via the quartz sensor 11. 1-20 by part 13
Controlled within the range of person/S. In this case, for a given titanium formation rate, an increase in the nitrogen ion beam density results in the formation of a reddish film, and conversely, an increase in the hydrocarbon gas ion beam density results in the formation of a blackish film. There was found.
このように、チタン（Ｔｉ）の形成速度に対する炭化水
素ガスと窒素ガスとのイオンビーム比を制御することで
、所定の膜組成構造を備えたＴｉＣＮ膜が再現性良く得
られた。In this way, by controlling the ion beam ratio of hydrocarbon gas and nitrogen gas to the formation rate of titanium (Ti), a TiCN film having a predetermined film composition structure was obtained with good reproducibility.
以上の条件にてＴｉＣＮ膜をカミソリ刃の表面に形成さ
せたところ、ビッカース硬度１５００〜３０００ＨＶ程
度の高硬度膜が得られ、刃の寿命改善を図ることができ
た。又、膜の色が黒色〜赤紫色〜銅色〜金色の領域にお
ける色調の制御も容易に行うことができた。更に、刃の
表面に形成されたＴｉＣＮ膜の耐食性を塩水噴霧テスト
によって評価したところ、下表−１で明らかなように、
従来のイオンブレーティングあるいはスパッタリングに
よる膜サンプルによれば、２〜３サイクル終了後に多量
のサビが発生したのに対し、本実施例のイオンビームア
シスト蒸着手段によれば、膜サンプルにはサビがほとん
ど発生しないことが確認された。When a TiCN film was formed on the surface of a razor blade under the above conditions, a highly hard film with a Vickers hardness of about 1,500 to 3,000 HV was obtained, and the life of the blade could be improved. Furthermore, the color tone of the film could be easily controlled in the range of black to reddish purple to coppery to gold. Furthermore, the corrosion resistance of the TiCN film formed on the surface of the blade was evaluated by a salt spray test, as shown in Table 1 below.
According to the film sample obtained by conventional ion blasting or sputtering, a large amount of rust occurred after 2 to 3 cycles, but according to the ion beam assisted vapor deposition method of this embodiment, there was almost no rust on the film sample. It has been confirmed that this does not occur.
（発明の効果）
以上説明した通り、本発明は、表面に被膜を形成すべき
刃を真空槽内に配置し、この刃に対し炭化水素ガスおよ
び窒素ガスのイオンビームをそれぞれ照射すると共に、
このイオンビーム照射と同時に蒸発源からチタンを電子
ビーム蒸発させ、チタンの形成速度に対する各イオンビ
ーム密度を制御しながら刃の表面にＴｉＣＮ膜を形成す
るようにしたことにより、耐食性に優れた硬質被膜を形
成することができる。(Effects of the Invention) As explained above, in the present invention, a blade on which a film is to be formed is placed in a vacuum chamber, the blade is irradiated with ion beams of hydrocarbon gas and nitrogen gas, and
At the same time as this ion beam irradiation, titanium is evaporated with an electron beam from an evaporation source, and a TiCN film is formed on the surface of the blade while controlling the ion beam density with respect to the titanium formation rate, resulting in a hard coating with excellent corrosion resistance. can be formed.
第１図は本発明方法を使用するための装置の概略構成を
示す図、第２図は従来の方法により刃の表面に被膜を形
成した場合の拡大断面図である。
４・・・電子ビーム蒸発源 ５．６・イオン銃９ ・・
刃 １０・・・真空チャンバ１１・・・
水晶センナ １３・・・膜形成速度制御部第
図
２ ＴｉＣＮ膜
１刃（ステンしス葛したｊ青λ豪十）FIG. 1 is a diagram showing a schematic configuration of an apparatus for using the method of the present invention, and FIG. 2 is an enlarged sectional view of a case where a coating is formed on the surface of a blade by a conventional method. 4...Electron beam evaporation source 5.6.Ion gun 9...
Blade 10...Vacuum chamber 11...
Crystal senna 13...Film formation speed control section Fig. 2 TiCN film 1 blade (stainless steel)
Claims (1)
に対し炭化水素ガスおよび窒素ガスのイオンビームをそ
れぞれ照射すると共に、このイオンビーム照射と同時に
蒸発源からチタンを電子ビーム蒸発させ、チタンの形成
速度に対する各イオンビーム密度を制御しながら刃の表
面にＴｉＣＮ膜を形成するようにしたことを特徴とする
刃の表面処理方法。The blade on which a film is to be formed is placed in a vacuum chamber, and the blade is irradiated with ion beams of hydrocarbon gas and nitrogen gas, and titanium is evaporated from an evaporation source with an electron beam at the same time as the ion beam irradiation. A method for surface treatment of a blade, characterized in that a TiCN film is formed on the surface of the blade while controlling each ion beam density with respect to the titanium formation rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63320840A JPH0759744B2 (en) | 1988-12-20 | 1988-12-20 | Blade surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63320840A JPH0759744B2 (en) | 1988-12-20 | 1988-12-20 | Blade surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02166270A true JPH02166270A (en) | 1990-06-26 |
| JPH0759744B2 JPH0759744B2 (en) | 1995-06-28 |
Family
ID=18125828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63320840A Expired - Lifetime JPH0759744B2 (en) | 1988-12-20 | 1988-12-20 | Blade surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0759744B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1577416A1 (en) * | 2004-03-16 | 2005-09-21 | Seiko Epson Corporation | Decorative article and timepiece |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62146255A (en) * | 1985-12-20 | 1987-06-30 | Citizen Watch Co Ltd | Ion planted black film |
| JPS63251129A (en) * | 1987-04-01 | 1988-10-18 | Daijietsuto Kogyo Kk | Coated cutting edge for cutting tools |
| JPS63250454A (en) * | 1987-04-06 | 1988-10-18 | Hitachi Ltd | Ion mixing method and device |
-
1988
- 1988-12-20 JP JP63320840A patent/JPH0759744B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62146255A (en) * | 1985-12-20 | 1987-06-30 | Citizen Watch Co Ltd | Ion planted black film |
| JPS63251129A (en) * | 1987-04-01 | 1988-10-18 | Daijietsuto Kogyo Kk | Coated cutting edge for cutting tools |
| JPS63250454A (en) * | 1987-04-06 | 1988-10-18 | Hitachi Ltd | Ion mixing method and device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1577416A1 (en) * | 2004-03-16 | 2005-09-21 | Seiko Epson Corporation | Decorative article and timepiece |
| US7261956B2 (en) | 2004-03-16 | 2007-08-28 | Seiko Epson Corporation | Decorative article and timepiece |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0759744B2 (en) | 1995-06-28 |
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